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Publication numberUS7553359 B2
Publication typeGrant
Application numberUS 11/596,941
PCT numberPCT/IB2005/001400
Publication dateJun 30, 2009
Filing dateMay 12, 2005
Priority dateMay 19, 2004
Fee statusPaid
Also published asCN1965035A, CN1965035B, DE602005023860D1, EP1753824A1, EP1753824B1, US20080194815, WO2005113684A1
Publication number11596941, 596941, PCT/2005/1400, PCT/IB/2005/001400, PCT/IB/2005/01400, PCT/IB/5/001400, PCT/IB/5/01400, PCT/IB2005/001400, PCT/IB2005/01400, PCT/IB2005001400, PCT/IB200501400, PCT/IB5/001400, PCT/IB5/01400, PCT/IB5001400, PCT/IB501400, US 7553359 B2, US 7553359B2, US-B2-7553359, US7553359 B2, US7553359B2
InventorsJordi Berenguer, Ludwig Hasemann, Joan Bosch, Susana Basolas
Original AssigneeClariant Finance (Bvi) Limited
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Stable liquid formulations of anionic dyes
US 7553359 B2
Abstract
The present invention concerns concentrated aqueous solutions of anionic disazo dyes, comprising salts and or the free acids of anionic dyes of the formula

and 2-(2-butoxyethoxy) ethanol wherein the substituents are each as defined in claim 1 and the use of these solutions for dyeing and/or printing hydroxyl-containing substrates and for producing inkjet inks.
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Claims(11)
1. A concentrated aqueous solution, comprising the salt or the free acid or mixtures thereof, of at least one anionic dye of the formula
wherein
D is a radical of the formula (a)
wherein
R1, R2, R3, are independently H; C1-4alkyl; C1-4alkoxy, SO3H; OH or CN; or independently SO2Y or OY, wherein Y is an unsubstituted C1-4-alkenyl group or an unsubstituted C1-4alkyl group or wherein Y is an NC, HO, HOSO3, halogen-substituted C1-4-alkenyl group or an NC, HO, HOSO3, halogen-substituted C1-4alkyl group or Y is NR11R12 wherein R11 and R12 are independently H, C1-4alkyl or substituted C1-4alkyl or combine with the interjacent nitrogen to form a five- or six-membered ring optionally comprising one or two or three heteroatoms, in which case the heterocyclic ring is unsubstituted or the heterocyclic ring is substituted by one or two C1-4alkyl groups,
or D is a bicyclic ring system unsubstituted or substituted with C1-4alkoxy, SO3H; OH or CN; or independently SO2Y or OY, wherein Y is an unsubstituted C1-4-alkenyl group or an unsubstituted C1-4alkyl group or wherein Y is an NC, HO, HOSO3, halogen-substituted C1-4-alkenyl group or an NC, HO, HOSO3, halogen-substituted C1-4alkyl group or Y is NR11R12 where R11 and R12 are each as defined above, wherein each of the rings are, optionally, and independently a five-membered or six-membered ring, wherein the five- or six-membered rings, optionally include one or two or three heteroatoms and this bicyclic ring system is not further substituted by substituents attached via azo groups, and
M is a bridging phenyl group unsubstituted or substituted by C1-4alkyl, C1-4alkoxy, hydroxyl, carboxyl, sulpho, cyano or halogen,
and
when n=1, B is hydrogen, an unsubstituted aryl radical, a substituted aryl radical, or a substituted triazine derivative of the formula
wherein X1 and X2 are independently unsubstituted amine NH2 or substituted amine NR21R22 wherein R21 and R22 are independently: H, C1-4alkyl or substituted C1-4alkyl, or combine with the interjacent nitrogen to form a five- or six-membered ring optionally comprising one or two or three heteroatoms, in which case the heterocyclic ring is unsubstituted or the heterocyclic ring is substituted by one or two C1-4alkyl groups
or when n=2, B is a bridge of the formula
or a bridge of the formula
where X1 is defined above
and 2-(2-butoxyethoxy) ethanol.
2. A concentrated aqueous solution according to claim 1, wherein the at least one dye of the formula I is a dye of the formula I′
3. A concentrated aqueous solution according to claim 1, wherein
D is a radical of the formula (a′)
wherein
R1, R2, R3, are independently H; C1-4alkyl C1-4 alkoxy; SO3H; OH or CN;
M is a bridging phenyl group unsubstituted or substituted by C1-4alkyl, C1-4alkoxy; sulpho, carboxyl, or hydroxyl and
B is H, an unsubstituted phenyl group or substituted phenyl group or a substituted triazine derivative of the formula
where X1 and X2 are independently as defined above and n=1.
4. A concentrated aqueous solution according to claim 1, wherein the concentrated aqueous solution comprises 5% to 40% by weight of the at least one dye of the formula I, 5-40% by weight of 2-(2-butoxyethoxy) ethanol and 20% to 90% by weight of water.
5. A concentrated aqueous solution according to claim 1, wherein the concentrated aqueous solution comprises 5% to 40% by weight of the at least one dye of the formula I, 5% to 40% by weight of 2-(2-butoxyethoxy) ethanol, 3-10% by weight of a water-soluble organic solubilizer and 10% to 88% by weight of water.
6. A concentrated aqueous solution according to claim 1, wherein the concentrated aqueous solution comprises 10% to 30% by weight of the at least one dye of the formula I, 10% to 30% by weight of 2-(2-butoxyethoxy) ethanol, 3-6% by weight of a water-soluble organic solubilizer and 34% to 77% by weight of water.
7. An inkjet ink comprising at least one concentrated aqueous solution according to claim 1.
8. A method for dyeing and/or printing a hydroxyl-containing substrate comprising the step of contacting at least one concentrated aqueous solution according to claim 1 with the hydroxyl-containing substrate.
9. A hydroxyl-containing substrate dyed and/or printed by the process according to claim 8.
10. A hydroxyl-containing substrate according to claim 9 wherein the hydroxyl-containing substrate is paper.
11. A method for producing an inkjet ink, comprising the step of combining a concentrated aqueous solution according to claim 1, with at least one additional chemical and/or water.
Description

The present invention concerns concentrated storage-stable aqueous dye solutions, especially concentrated storage-stable aqueous dye solutions comprising anionic disazo dyes. The invention further concerns the use of the present invention's concentrated dye solutions, if appropriate after dilution with water, especially for dyeing and printing paper, including card and board. The invention likewise concerns the production of printing inks, especially inkjet printing inks, by using the concentrated dye solutions of the present invention.

Industrial dyeing and printing is customarily carried out in an aqueous medium. So pulverulent dyes first have to be dissolved, usually in warm or hot water, to be able to use them for printing and dyeing.

Metering systems have been developed in recent years to control the addition of dye by weighing or volumetrically, and they often require stable dye solutions instead of powders and granules.

Such dye solutions also have the advantage that they do not dust and do not require costly dissolving operations.

Such solutions should possess a certain stability, so that they do not precipitate during transportation or storage. Typically, they should be stable for a prolonged period between zero and five degrees Celsius, but also at around 50 C. Similarly, frozen solutions shall be stable after thawing and should not present any stability problems during pumping. Solutions containing precipitates can cause disruptions in pumping or metering systems and lead to unacceptable machine shutdowns and costly cleaning and maintenance.

The present invention accordingly provides concentrated aqueous solutions of anionic disazo dyes, comprising salts and or the free acids of anionic dyes of the formula


where

    • D is a radical of the formula (a)

      • where
      • R1, R2, R3, are independently H; C1-4alkyl; C1-4alkoxy, SO3H; OH or CN; or independently SO2Y or OY, wherein Y is an unsubstituted C1-4alkenyl group or an unsubstituted C1-4alkyl group or wherein Y is an NC, HO, HOSO3, halogen-substituted C1-4-alkenyl group or an NC, HO, HOSO3, halogen-substituted C1-4alkyl group or Y is NR11R12 where R11 and R12 are independently H, C1-4alkyl or substituted C1-4alkyl or combine with the interjacent nitrogen to form a five- or six-membered ring which may comprise one or two or three heteroatoms (one or two N, O or S atoms in addition to the nitrogen), in which case the heterocyclic ring is unsubstituted or the heterocyclic ring is substituted by one or two C1-4alkyl groups,
      • or D is a bicyclic ring system which may be substituted with C1-4alkoxy, SO3H; OH or CN; or independently SO2Y or OY, wherein Y is an unsubstituted C1-4alkenyl group or an unsubstituted C1-4alkyl group or wherein Y is an NC, HO, HOSO3, halogen-substituted C1-4-alkenyl group or an NC, HO, HOSO3, halogen-substituted C1-4alkyl group or Y is NR11R12 where R11 and R12 are each as defined above, wherein each of the rings can independently be a five-membered or six-membered ring and these five- or six-membered rings, which may include one or two or three heteroatoms (one or two N, O or S atoms in addition to nitrogen) and this bicyclic ring system is not further substituted by substituents attached via azo groups, and
    • M is a bridging phenyl group which may be unsubstituted or substituted by C1-4alkyl, C1-4alkoxy, hydroxyl, carboxyl, sulpho, cyano or halogen, and
    • when n=1 B is hydrogen, an unsubstituted aryl radical, a substituted aryl radical, or a substituted triazine derivative having the formula

    • where X1 and X2 are independently unsubstituted amine NH2 or substituted amine NR21R22 where R21 and R22 independently have the following meanings: H, C1-4alkyl or substituted C1-4alkyl, or combine with the interjacent nitrogen to form a five- or six-membered ring which one or two or three heteroatoms (one or two N, O or S atoms in addition to the nitrogen), in which case the heterocyclic ring is unsubstituted or the heterocyclic ring is substituted by one or two C1-4alkyl groups
    • or when n=2 B is a bridge of the formula

      • or a bridge of the formula

      • where X1 is as defined above
        and 2-(2-butoxyethoxy) ethanol.

Alkyl as used herein is to be understood as meaning generally straight-chain or branched alkyl groups. These preferably have 1 to 4 carbon atoms. They are for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or tert-butyl.

Suitable alkoxy radicals are preferably those having 1 to 4 carbon atoms, for example methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy or tert-butoxy.

Suitable substituents for arylradicals and/or phenyl radicals are C1-4alkyl, C1-4alkoxy, hydroxyl, carboxyl, sulpho, cyano or halogen.

Halogen is fluorine, bromine, iodine or chlorine. Chlorine is the preferred halogen.

The aryl radicals constitute aromatic carbocyclic or heterocyclic radicals and can also be for example bicyclic, for example pyridyl, naphthyl or phenyl. Phenyl is particularly preferred. In the case of a bicyclic ring system each of the rings may independently be a five-membered or six-membered ring and these five- or six-membered rings, which may include one or two or three heteroatoms (one or two N, O or S atoms in addition to the nitrogen), can be further substituted like the monocyclic substituents by C1-4alkyl; C1-4alkoxy, SO3H; OH or CN; or independently SO2Y or OY, wherein Y is an unsubstituted C1-4alkenyl group or an unsubstituted C1-4alkyl group or wherein Y is an NC, HO, HOSO3, halogen-substituted C1-4alkenyl group or an NC, HO, HOSO3, halogen-substituted C1-4alkyl group or Y is NR11R12 where R11 and R12 are independently H, C1-4alkyl or substituted C1-4alkyl or combine with the interjacent nitrogen to form a five- or six-membered ring which may comprise one or two or three heteroatoms (one or two N, O or S atoms in addition to the nitrogen), in which case the heterocyclic ring is unsubstituted or the heterocyclic ring is substituted by one or two C1-4alkyl groups.

Suitable anionic disazo dyes are preferably those of the formula


where the substituents are each as defined above.

In a preferred embodiment the substituents have the following meanings:

    • D is a radical of the formula (a′)

      • where
      • R1, R2, R3, are independently H; C1-4alkyl C1-4alkoxy; SO3H; OH or CN;
    • M is a bridging phenyl group which may be unsubstituted or substituted by C1-4alkyl, C1-4alkoxy; sulpho, carboxyl, hydroxyl and
    • B is H, an unsubstituted phenyl group or substituted phenyl group or a substituted triazine derivative of the formula

    • where X1 and X2 are independently as defined above and n=1.

By preference B is H, an unsubstituted phenyl group or substituted phenyl group.

Very particular preference is given to anionic disazo dyes of the formula (I′) where

    • D is a phenyl group of the formula (a″)

      • where R1, R2, R3, are independently H; C1-2alkyl; C1-2 alkoxy; SO3H; M is a bridging phenyl group by C1-2alkyl, C1-2alkoxy and sulpho substituted can be and B is an unsubstituted phenyl group and n=1

In particularly preferred anionic disazo dyes there is a sulpho group in the phenyl group D. In particularly preferred anionic disazo dyes the alkyl groups are methyl groups and the alkoxy groups are methoxy groups.

In particularly preferred anionic disazo dyes the middle component is a para-substituted phenyl group, i.e. bridging in position 1-4.

The solutions according to the present invention may comprise further components such as for example water-soluble organic solubilizers and/or biocides.

Suitable water-soluble organic solubilizers are for example urea, formamide, dimethylformamide, water-miscible polyhydric alcohols such as ethylene glycol, propylene glycol, glycerol, alkanolamines such as ethanolamine, triethanolamine. The preferred water-soluble organic solubilizer is triethanolamine.

The suitable water-soluble organic solubilizers are added in an amount of 0% to 15% by weight, more preferably in an amount of 2% to 10% by weight and most preferably in an amount of 3% to 6% by weight.

Any biocide is suitable. But preference is given to using biocides having FDA and/or BGVV approval. Any biocide capable of controlling the growth of Gram-positive or Gram-negative bacteria, yeasts or fungi can be used in the solutions of the present invention. Suitable biocides are for example thiazol-3-one derivatives, for example alkyl and/or chlorinated thiazol-3-one derivatives or mixtures thereof. Typically, the biocides are used in an amount of 15 parts by weight per million parts of the composition (ppm) up to 1000 ppm; particular preference is given to 50 ppm to 500 ppm (parts by weight per ready-produced composition).

The concentrated solutions of the present invention are generally produced by stirring the free dye acids with a mixture of water and 2-(2-butoxyethoxy) ethanol until a homogeneous solution forms.

The amount of polyglycolamine in the mixture can vary within wide limits, so that (relative to the amount required for complete salt formation) a deficiency or excess can be present. Preferably, however, at least the amount required for complete salt formation is used.

The stable solutions of the present invention comprise preferably not less than 10% by weight of (2-(2-butoxyethoxy)ethanol. The stable solutions of the present invention comprise not less than 10% by weight of (2-(2-butoxyethoxy)ethanol and not less than 3% by weight of a water-soluble organic solubilizer in particularly preferred embodiments.

The solutions generally comprise:

  • 5-40% by weight of anionic dye (reckoned as free acid),
  • 5-40% by weight of 2-(2-butoxyethoxy) ethanol, and
  • 20-90% by weight of water.

Preferred concentrated solutions comprise

  • 10-30% by weight of dye,
  • 10-30% by weight of 2-(2-butoxyethoxy) ethanol, and
  • 40-80% by weight of water.

When the solutions of the present invention additionally comprise solubilizer, the composition of the solutions according to the present invention will generally be

  • 5-40% by weight of anionic dye (reckoned as free acid),
  • 5-40% by weight of (2-(2-butoxyethoxy)ethanol,
  • 3-10% by weight of a water-soluble organic solubilizer, and
  • 10-88% by weight of water.

Preferred concentrated solutions comprise

  • 10-30% by weight of dye,
  • 10-30% by weight of (2-(2-butoxyethoxy)ethanol,
  • 3-6% by weight of a water-soluble organic solubilizer, and
  • 34-77% by weight of water.

The concentrated solutions of the present invention are notable especially for excellent stability in storage and for a low viscosity at room temperature and temperatures below room temperature, for example at 0-5 C. More particularly, the concentrated solutions of the present invention are stable even when they are kept frozen at −20 C. for 2 days and after thawing they remain stable at 0-5 C. or else at 25 C. and at 50 C. for 14 days without any signs of precipitation. The viscosity of the concentrated solutions according to the present invention increases only insignificantly, if at all, when cooling down to just short of freezing, so that they are readily meterable at low temperatures as well as at normal temperatures.

The concentrated dye solutions of the present invention are used, if appropriate after dilution with water, for dyeing and/or printing hydroxyl-containing substrates. More particularly, the solutions of the present invention are used for dyeing paper, including card and board, these materials being dyeable in the pulp, by coating or by dipping for example. Besides, such a liquid formulation can also be used for a continuous or batch dyeing process for textile materials, especially cellulose.

The invention also comprises hydroxyl-containing substrates which have been dyed and/or printed with the present invention's concentrated dye solutions, if appropriate after dilution with water. More particularly, the invention also comprises paper, including card and board, dyed and/or printed with the concentrated dye solutions of the present invention. Besides, such a liquid formulation can also be used for a continuous or batch dyeing process for textile materials, especially cellulose.

In addition, the concentrated dye solutions of the present invention are useful as colorants in aqueous and non-aqueous inkjet inks and also in hotmelt inks.

Inkjet inks comprise in general a total of 0.5 to 15% by weight, and preferably 1.5% to 8% by weight (reckoned dry, i.e. reckoned back to the pure dye content) of one or more of the concentrated dye solutions of the present invention.

Microemulsion inks are based on organic solvents and water with or without an additional hydrotropic substance (interface mediator). Microemulsion inks comprise in general from 0.5% to 15% by weight, preferably from 1.5% to 8% by weight of one or more of the concentrated dye solutions of the present invention, 5% to 99% by weight of water and 0.5% to 94.5% by weight of organic solvent and/or hydrotropic compound.

Solvent-borne inkjet inks comprise preferably 0.5% to 15% by weight of one or more of the concentrated dye solutions of the present invention, 85% to 99.5% by weight of organic solvent and/or hydrotropic compounds.

Hotmelt inks are usually based on waxes, fatty acids, fatty alcohols or sulphonamides which are solid at room temperature and liquefy on heating, the preferred melting range being between about 60 C. and about 140 C. Hotmelt inkjet inks consist for example essentially of 20% to 90% by weight of wax and 1% to 10% by weight of one or more of the concentrated dye solutions of the present invention. They may further include 0% to 20% by weight of an additional polymer (as a dye dissolver), 0% to 5% by weight of dispersing assistant, 0% to 20% by weight of viscosity modifier, 0% to 20% by weight of plasticizer, 0% to 10% by weight of tackifier, 0% to 10% by weight of transparency stabilizer (prevents crystallization of waxes for example) and also 0% to 2% by weight of antioxidant. The concentrated dye solutions of the present invention are further useful as colorants for colour filters, not only for additive but also for subtractive colour production and also as colorants for electronic inks (e-inks) or electronic paper (e- paper).

The examples which follow illustrate the invention. All % data in the description and in the examples are to be understood as % by weight, unless otherwise stated.

EXAMPLE 1

400 g of the dye of the formula


are dissolved in 6000 ml of demineralized water by addition of sufficient triethenolamine for a pH of 8 to 9 and are desalted and concentrated to a weight of 3045 g by membrane filtration at temperatures of 20-50 C., and preferably between 30 and 40 C. and pressures of from 10-40 bar, and more preferably of 20-30 bar.

410 g of concentrated dye solution are then admixed with 75 g of 2-(2-butoxyethoxy) ethanol, 15 g of triethanolamine and 0.75 g of biocide (Proxel GXL; Proxel is a trade mark of Zeneca AG Products, Inc. and comprises 1,2-benzisothiazolin-3-one (CAS No.: 2634-33-5)) and diluted to 500 g with demineralized water and stirred until homogeneous.

The solution obtained is stable in storage in that it neither thickens nor separates under the following conditions: 2 days −20 C. and thawing; 14 days at 0-5 C., at 25 C. and at 50 C.

EXAMPLE 2

410 g of the concentrated dye solution of Example 1 are admixed with 50 g of 2-(2-butoxyethoxy) ethanol, 25 g of triethanolamine and 0.75 g of biocide and diluted to 500 g with demineralized water and stirred until homogeneous.

The solution obtained is stable in storage in that it neither thickens nor separates under the test conditions.

EXAMPLES 3-18

Stable concentrated solutions of the following dyes are preparable in the same way as described in Examples 1 and 2

Ex D M KK B n
3 1
4 1
5 1
6 1
7 1
8 H 1
9 1
10 1
11 1
12 1
13 1
14 1
15 1
16 1
17 2
18 2

Dyeing Prescription A

70 parts of chemically bleached pinewood sulphite cellulose and 30 parts of chemically bleached birchwood sulphite cellulose are beaten into 2000 parts of water in a hollander. 1.5 parts of the liquid dye preparation of Example 1 are added to the stuff. Paper is made therefrom after a mixing time of 20 minutes. The absorbent paper obtained in this way has a bluish violet colour.

Dyeing Prescription B

1.5 parts of the liquid dye preparation of Example 1 are added to 100 parts of chemically bleached sulphite cellulose beaten with 2000 parts of water in a hollander. After mixing through for 15 minutes, customary sizing is effected using resin size and aluminium sulphate. Paper made from this material exhibits a bluish violet hue in each case.

Dyeing Prescription C

An absorbent web of unsized paper is pulled at 40-50 C. through an aqueous dye solution consisting of 95 parts of water and 5 parts of the inventive dye solution of Example 1.

Excess dye solution is squeezed by two rolls. The dried web of paper has a bluish violet colour in each case.

The dye preparations of Examples 2 to 18 can be used for dyeing similarly to prescriptions A to C.

Dyeing Prescription D

5 parts of the dye preparation of Example 1 are metered into 4000 parts of softened water at room temperature. 100 parts of prewetted woven cotton fabric are introduced into the bath, followed by heating to the boil over 30 minutes. The bath is held at the boil for an hour during which evaporated water is made good from time to time. The dyeing is then removed from the liquor, rinsed with water and dried. The dyeing obtained has a bluish violet colour.

The dye preparations of Examples 2-18 can be used for dyeing cotton in a similar manner.

Dyeing Prescription E

100 parts of freshly tanned and neutralized chrome grain leather are drummed for 30 minutes in a float of 250 parts of water at 55 C. and 0.5 part of the dye preparation made according to Example 1 and are treated for a further 30 minutes in the same bath with 2 parts of an anionic fatliquor based on sulphonated fish oil. The leathers are conventionally dried and finished. The leather obtained has a level scarlet hue.

Further low-affinity, vegetable-retanned leathers can likewise be dyed according to known methods.

Dyeing can be done in a similar manner with the dyes of Examples 2-18.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
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Non-Patent Citations
Reference
1English Abstract for JP 02 127483, May 1990.
2English Abstract for JP 10 292140, Nov. 1998.
3English abstract for JP 2003 246950, Sep. 2003.
4PCT International Search Report for PCT/IB2005/001400, dated Aug. 12, 2005.
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US8328925May 21, 2008Dec 11, 2012Clariant Finance (Bvi) LimitedStable liquid formulation
Classifications
U.S. Classification106/31.52, 8/681, 106/31.5, 106/31.48, 8/687
International ClassificationC09B67/26, C09B31/08, C09B67/44, C09D11/02, C09D11/00
Cooperative ClassificationC09B67/0073, C09B67/0083, C09D11/328, C09D11/54, C09D11/32
European ClassificationC09D11/32, C09D11/328, C09D11/54, C09B67/00P9, C09B67/00P2B
Legal Events
DateCodeEventDescription
Oct 22, 2012FPAYFee payment
Year of fee payment: 4
Nov 17, 2006ASAssignment
Owner name: CLARIANT FINANCE (BVI) LIMITED, VIRGIN ISLANDS, BR
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BERENGUER, JORDI;HASEMANN, LUDWIG;BOSCH, JOAN;AND OTHERS;REEL/FRAME:018602/0696
Effective date: 20060828